CN105358119A - Hardenable dental composition containing a mixture of agglomerated and aggregated nano-particles, kit of parts and use thereof - Google Patents

Abstract

The invention relates to a dental composition comprising - filler (F1) comprising aggregated nano-sized particles in an amount of from about 30 to about 70 wt.%, - filler (F2) comprising agglomerated nano-sized particles in an amount from about 1 to about 20 wt.%, - hardenable component (A1) being an urethane(meth)acrylate with a functionality of at least 2 and having a molecular weight from about 400 to about 3,000 g/mol, - hardenable component (A2) being a radically polymerizable (meth)acrylate with a functionality of at least 2 being different from component (A1), - redox curing initiator system, the dental composition not comprising non-agglomerated nano-sized filler in an amount above about 10 wt.%, wt.% with respect to the weight of the whole composition The dental composition is in particular useful as or for production of permanent crown and bridges, inlays, onlays and veneers.

Description

Comprise the hardenable dental compositions of the mixture of the nanoparticle of cohesion and gathering, assembly cover box and uses thereof

Technical field

The present invention relates to a kind of dental composition, this dental composition can be used as dental filling material, particularly as packing material in bulk or for the preparation of the long-term repair body being similar to persistency compound corona and bridge, insert, onlay and veneer.

Background technology

Composite is well known in stomatology, and can be used for such as packing material, persistency cement or provisional corona and bridge material.According to indication, different composites is distinguished by its corresponding filler content.

Filled composite is generally high filler loading capacity material, it is characterized in that good mechanical performance, as low abrasion (low wear intensity).Regrettably, due to high amount of filler, these materials are sometimes frangible.

Compared to filled composite, provisional corona and bridge material have lower filer content.This usually makes elasticity improve and rupture strength is higher, but the thing followed is that abrasion or wear intensity increase usually, which hinders the life-time service of these materials.

Commercially available laboratory composite for the manufacture of dental prosthesis such as corona cannot be used for the operation on office or chair limit, and needs the participation of outside dental laboratory.Alternatively, composite grinding block such as Paradigm ^tMmZ100 (3MESPE) can be used for the operation on office or chair limit, but the CAD/CAM technology needing investment quite expensive.

Therefore, need a kind of material, this material combines and above-mentionedly can be used for the compound corona on office or chair limit and the material behavior of bridge manufacture and without the need to investing CAD/CAM technology.In addition, patient and odontologist are now growing to the demand of persistency dental prosthetic.

EP2167013A1 (3M) relates to the dental composition and preparation and application thereof that comprise multifunctional (methyl) acrylate be made up of carbamate, carbamide or amide groups.

US2005/0234148A1 (Heraeus) describes the inorganic filler of the cohesion for dental materials, this inorganic filler comprises 0.5 μm to 50 μm condensation product of 200nm to 7000nm inorganic particulate, and these particles and at least one adjacent particles are in its interface consolidation.WO2012/057917A1 (3M) describes preformed semi-finished product dental articles, it comprises uncured dental restorative compositions, this dental restorative compositions comprises the specific resin system accounting for nanocluster fillers at least 50 % by weight, wherein uncured dental restorative compositions has the first shape, and the ductility of this first shape is enough to make it form the second shape.

US6,730,156B1 (people such as Windisch) relate to the filler comprising and be essentially amorphous cluster, and it comprises non-heavy oxygen compound particle and heavy metallic oxide.This filler can with can mix by hardening resin, to provide the ray with desirable strength and aesthetic features can not dental materials thoroughly.

Summary of the invention

Particularly, expect that available dental composition has high breaking strength, low wear intensity and enough pliabilities.If possible, dental composition also should be easy to use.Ideally, dental composition should be also attractive in appearance and acceptable.

This target is achieved by dental composition as herein described.

In one embodiment of the invention, provide a kind of dental composition, this dental composition comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight, this filler comprises the nanometer particle of gathering,

The filler (F2) of-Yue 1 % by weight to about 20 % by weight, this filler comprises the nanometer particle of cohesion,

-can hardenable component (A1), it is have the degree of functionality carbamate (methyl) acrylate with the molecular weight higher than about 450g/mol that are at least 2,

-can hardenable component (A2), it is at least 2 and (methyl) acrylate being different from the free redical polymerization of the degree of functionality of component (A1) for having,

-Redox initiator systems or dark curing initiator system.

This dental composition does not comprise the nano-sized filler (such as, particle mean size is lower than about 50nm) of non-cohesion of amount higher than about 10 % by weight usually.

The invention still further relates to a kind of assembly cover box, this assembly cover box comprises dental composition as herein described and with at least one in lower component or all:

-device for mixing,

-dental impression material,

-dental cement.

The invention still further relates to use dental composition as herein described as or for the preparation of corona, bridge, insert, onlay, veneer and as packing material in bulk.

definition

Unless defined differently, otherwise for this description, following term should have given implication:

" dental composition " or " compositions for dental use " or " being ready to use in the compositions in dental field " is for can be used for any compositions in dental field.In this, compositions should be harmless to patient health and not contain danger and the poisonous component that can shift out from compositions.The example of dental composition comprises permanent and provisional corona and bridge material, artificial corona, labial teeth or backteeth packing material, binding agent, grinding base, lab material and orthodontic device.Dental composition is generally hardenable compositions, and it can harden at ambient conditions, the temperature range of about 15 DEG C to 50 DEG C or about 20 DEG C to 40 DEG C in the time range that this environmental condition is included in about 30 minutes or 20 minutes or 10 minutes.Do not recommend higher temperature, because they may cause the pain of patient and may damage the health of patient.Dental composition is supplied to practitioner with less volume usually, and namely volume is in the scope of about 0.1mL to about 100mL or about 0.5mL to about 50mL or about 1mL to 30mL.Therefore, the reservoir volume of used pack device is within the scope of these.

" can hardenable component or material " or " polymerizable components " for can such as by heating with any component causing polymerization, chemical crosslinking, radiation-induced polymerization or solidify by using being cross-linked of redox initiator or harden.Can comprise an only one, two, three or more polymerizable groups by hardenable component.The representative instance of polymerizable groups comprises unsaturated carbon group, is such as especially present in the vinyl groups in (methyl) acrylic." initiator " is for starting or cause the material of the solidification process of hardenable compositions.

" monomer " for useful chemical formula characterize with can be grouped to oligomer or polymer thus increasing any chemical substance of the polymerizable groups (comprising (methyl) acrylic) of molecular weight.The molecular weight of monomer can calculate based on given chemical formula usually simply.

As used herein, " (methyl) acryloyl " is breviary term, and it refers to " acryloyl " and/or " methacryl ".Such as, " (methyl) acryloxy " is breviary term, and it refers to acryloxy (that is, CH ₂=CH-C (O)-O-) and/or methacryloxy (that is, CH ₂=C (CH ₃)-C (O)-O-).

" solidification, sclerosis or setting reaction " is used interchangeably, and refers to physical characteristic (such as viscosity and hardness) the time dependent reaction due to the chemical reaction between each component of wherein compositions.

" comprise the polymerizable components of acidic-group " and be intended to comprise monomer, oligomer and the polymer with ethylenic unsaturated functional group and acid functional group and/or acidic precursor functional group.Acidic precursor functional group comprises such as anhydride, carboxylic acid halides and pyrophosphate.Acidic-group preferably comprises one or more carboxylic acid residues such as-COOH or-CO-O-CO-, phosphate moiety such as-O-P (O) (OH) OH, residue such as C-P (O) (OH) OH, sulfonic acid moieties such as-SO ₃h or sulfinic acid residue such as-SO ₂h.

The drying that " powder " means to be made up of a large amount of very thin particles, accumulated solids, described particle can free-flow when being vibrated or tilting.

" particle " represents to have the solid matter geometrically can determining its shape.Usually such as particle can be analyzed according to granularity or diameter.

The particle mean size of powder can be obtained by the cumulative curve of particle size distribution, and particle mean size is defined as the arithmetic mean of instantaneous value of the granularity of some mixture of powders recorded.Corresponding measurement can use the particle size analyzer of commercially available acquisition (such as, CILAS laser diffraction granularity analyser) to carry out.

" nano-sized filler " has the size in nano-area for a kind of filler, its single particle, such as, be less than about 200nm or be less than about 100nm or be less than the mean diameter of about 50nm.US6,899,948 and US6,572,693 give available example, and the content especially about nanosized silica particles is incorporated herein by reference.

The measurement of the size of nanoparticle is preferably based on TEM (transmission electron microscope) method, analyzes overall to obtain mean diameter thus.The method for optimizing measuring particle diameter can describe as follows:

Sample thick for about 80nm is placed on there is the stable polyvinyl formal substrate of carbon (Pennsylvania west chester (WestChester, PA) department of SPISupplies-structure probe company (StructureProbe, Inc)) 200 order copper mesh on.JEOL200CX (originate from the JEOL company limited of Japanese Zhao Dao city (Akishima) and sold by JEOL company of the U.S.) is used to take transmission electron micrograph (TEM) at 200kV.Then the overall dimension can measuring an about 50-100 particle determines mean diameter.

" cohesion " is to the usual description being kept also can fragmenting into the weak association of the particle of less entity by electric charge or polarity.The specific surface area of aggregated particle does not depart from the specific surface area of the primary particle forming condensation product substantially (see DIN53206; 1972).

The commercially available acquisition of cohesion filler, such as, with trade name Aerosil ^tM, CAB-O-SIL ^tMwith HDK purchased from goldschmidt chemical corporation (Degussa), Cabot Co., Ltd (CabotCorp) or Wa Ke company (Wacker).

" non-cohesion filler " refer to filler grain in resin with discrete, without (i.e. non-cohesion and non-agglomerated) the form existence of associating.If needed, verify by TEM microscopic method.

The commercially available acquisition of nanometer grade silica of non-cohesion, such as with the Nalco Chemical Co of trade name NALCOCOLLOIDALSILICAS purchased from American Illinois Na Boweier (NalcoChemicalCo. (Naperville, Ill.)), such as, NALCO product #1040,1042,1050,1060,2327 and 2329.Non-cohesion filler use and description sees in such as EP2167013B1 (3M).The content of the document is incorporated to herein by reference.

" gathering " used herein is to usually by such as residue chemistry process or the description of strong association partially sintering the particle combined; The specific surface area of aggregate particles is less than the specific surface area of the primary particle forming condensation product usually (see DIN53206; 1972).

Aggregation is decomposed into during less entity can occur in the polishing step putting on the surface comprising the compositions of assembling filler further, but does not occur in process aggregate particles be distributed in resin.

Assemble filler and preparation technology and surface treatment thereof at such as WO01/30304 and US6, described by having in 730,156 (3M).The content of these files is incorporated to herein by reference.

" be dispersed in resin in " refer to filler grain in resin with cohesion or assemble or discrete (that is, without associate, non-cohesion and non-agglomerated) particulate forms exists.

" carbamate groups " refers to the group with structure "-NH-CO-O-".

" urea group " refers to the group with structure "-NH-CO-NH-".

" amide groups " refers to the group with structure "-NH-CO-".

" unit " is the single formation block of chemical molecular or its minor structure.Individual unit is connected to each other.Typical unit comprises: CH ₃-,-CH ₂-,-O-,-S-,-NR ¹-,-CO-,-CR ¹=, -N=,-CR ¹r ²-, wherein R ¹and R ²independently selected from hydrogen, linear alkyl groups (comprises C1, C2, C3, C4, C5, C6 group), the alkyl group replaced (comprises C1, C2, C3, C4, C5, C6 group), alkenyl group (comprises C1, C2, C3, C4, C5, C6 group), group of naphthene base (comprising C4 to C14 group), the group of naphthene base (comprising C4 to C14 group) replaced, aromatic yl alkyl group (comprising C7 to C20), aromatic yl group (comprising C6 to C14) or the aromatic yl group (comprising C7 to C20) replaced.These unit can form straight chain, side chain or circulus, such as alkyl, cycloalkyl, aryl, ester group, carbamate groups or amide groups.

" coupling part " refers to the part of serving as and connecting and comprising the center of each (methyl) acrylate of side chain.Coupling part can have ring-type or branched structure.Coupling part even can be single atom, comprises N.If coupling part has circulus, it can be saturated, undersaturated or aromatic series homoatomic ring, namely, it only comprises the hydrocarbon unit of hydrocarbon or replacement, or it can be saturated, undersaturated or heteroaromatic, that is, it comprises hydrocarbon unit and at least one hetero atom of hydrocarbon or replacement, and this hetero atom comprises-O-,-N=,-NH-,-NR ¹-and/or-S-.If coupling part has branched structure, it comprises central atom as C or N, and at least three or four independent (methyl) acrylate comprising side chain extend from this central atom.Independent of the chemical constitution of coupling part, independent (methyl) acrylate comprising side chain can be symmetry or asymmetric relative to the arrangement of coupling part.

" spacer groups " for connecting the group of at least two other groups in the molecule of chemical formula.This group can be replacement or unsubstituted carbochain, and it also can comprise hetero atom (comprising O, N and S) or functional group as carbonyl group.

" dental impression material " is the material of the die for the manufacture of the tooth structure comprising gums.Dental impression material is administered to dental impression tray usually.Dental impression material can be undertaken being cross-linked (comprising addition curing and condensation cured material) by various chemical reaction based on different chemical substances.Typical example comprises siloxy group impression material (such as, VPS material) and polyether-based impression material and their mixture.

" provisional corona and bridge material " refer to for the preparation of dental corona and bridge can hardened material.These materials use usually need the time period of preparing persistency dummy such as corona and bridge Dental Technician during.Sustainable several days of this time period (1 day to about 6 days), a few week (1 thoughtful about 4 weeks) or some months (1 month to about 6 months).Chronicity corona and bridge material can use the time of about 6 months to 24 months usually.

Compared to chronicity corona and bridge material, " persistency corona and bridge material " can use more than 2 years and especially more than time of 5 years.Term " visible ray " is used in reference to has the light of about 400 nanometers (nm) to about 800 nanometer (nm) wavelength.

" environmental condition " refers to that the present composition is in the condition stored and usually stand during process.Environmental condition can be the pressure of such as about 900 millibars to about 1100 millibars, the temperature of about-10 DEG C to about 60 DEG C and the relative humidity of about 10% to about 100%.In the lab by ambient conditions extremely about 23 DEG C and about 1013 millibars.At dentistry and orthodontic fields, environmental condition is rationally interpreted as the pressure of about 950 millibars to about 1050 millibars, the temperature of about 15 DEG C to about 40 DEG C and the relative humidity of about 20% to about 80%.

As used in this article, " one ", " one ", " described ", " at least one " and " one or more " are used interchangeably.Term " comprise " or " containing " and version occurs in the specification and in the claims time the not conditional implication of tool.Term " comprise " also comprise more restricted expression " substantially by ... composition " and " by ... form ".

In addition, in this article, the numerical range defined by end points to comprise within the scope of this contained all numerical value (e.g., 1 to 5 comprise 1,1.5,2,2.75,3,3.80,4,5 etc.).Odd number and plural form should be comprised for term interpolation plural form means this term.Such as, term " one or more additives " means a kind of additive and more kinds of additive (such as, 2,3,4 etc.).

Except as otherwise noted, otherwise the amount of the expression composition used in description and claims, all numerals such as to measure as physical property described below be all interpreted as in all cases being modified by term " about ".

Detailed description of the invention

Find, compositions as herein described meets the demand of practitioner, especially about the demand of the such as balance of high-wearing feature (that is, low wear intensity), enough characteristics such as pliability and high breaking strength.Different fillers is combined with certain amount and combines with specific resin matrix to make it possible to be provided in and on the one hand there is high amount of filler and the compositions on the other hand with good treatment characteristic and balanced physical characteristic.

This target is normally difficult to realization.High amount of filler is usually along with the problem of the compositions pliability deficiency after the characteristic being difficult to mix and sclerosis.On the other hand, low sizing consumption is usually conducive to mixing and can contributes to better pliability, but usually causes wearability not enough.

Due to its viscosity characteristics, said composition is also easy to use, because it can be undertaken mixing and distributing by known mixing and distribution system.If need, this characteristic by as detailed below extrude test to verify.Compositions as herein described enables practitioner provide a kind of dental prosthesis for patient, and this dental prosthesis can use the longer time compared to existing provisional or chronicity corona and bridge material.Said composition not only can be used for preparation chronicity corona and bridge, and can be used for preparing insert, onlay and veneer based on composite.It also can be used as packing material in bulk.

In addition, this dental prosthesis can be prepared on chair limit, that is, without the need to the participation of dental laboratory.And without the need to the CAD/CAM technology of capital intensive.Dental composition as herein described comprises at least two kinds of fillers, i.e. filler (F1) and filler (F2).The feature of dental composition is relatively high amount of filler.In contrast, relative to the weight of whole compositions, the amount of filler of typical provisional corona and bridge material is in the scope of about 30 % by weight to about 40 % by weight.It is found that, high amount of filler is conducive to improving wearability, thus can provide the dental materials that can use for a long time in patient oral cavity.Filler (F1) comprises the nanometer particle of gathering.The chemical property of filler (F1) is not particularly limited, as long as can realize earmarking.

According to an embodiment, the feature of filler (F1) be in following characteristics at least one or all:

-specific surface area: about 50m ²/ g to about 400m ²/ g or 60m ²/ g to about 300m ²/ g or 80m ²/ g to about 250m ²/ g,

-comprise SiO2 particle, ZrO2 particle and their mixture.

If needed, specific surface area can use the device (Monosorb) purchased from Kang Ta instrument company (Quantachrome) to measure according to Bu Lunuo-Amy spy-Taylor (BET) formula.

If needed, particle mean size can be used and such as be measured by light scattering purchased from the MalvernMastersizer2000 device of Malvern instrument company (MalvernInstruments).Filler (F1) can according to such as WO01/30304 or US6, and 730, prepared by the technique described in 156.

Filler (F1) can be prepared by suitable colloidal sol and the heavy metal compound solution precursors comprising one or more oxygen, and described precursor can be salt, colloidal sol, solution or nanometer particle, wherein preferred sols.For the present invention, " colloidal sol " refers to colloidal solid particles stabilising dispersions in a liquid.The density of solids is greater than surrounding liquid usually, and granularity is enough little, makes dispersion force be greater than gravity.In addition, the size of this particle is enough little, makes them generally not reflect visible ray.Choose reasonable precursor sol obtains required vision opacity and intensity etc.The factor affecting colloidal sol selection depends on the combination of following characteristic: a) average-size of each particle, and its particle diameter is preferably less than about 100nm; B) acid: the pH of colloidal sol should preferably lower than about 6, and more preferably lower than about 4; And c) colloidal sol should be free from foreign meter, these impurity cause the particle of various discrete that excessive gathering (in filler preparation process) occurs in subsequent step such as spraying dry or calcination process, the particle that the particle diameter that formation may not easily disperse or exchange is larger, thus cause translucence and polishability to decline.

If initial colloidal sol is alkalescence, then should by such as adding nitric acid or other suitable acid carries out acidify to reduce pH.But, select alkaline initial colloidal sol to be more worthless, because it needs additional step and can cause introducing less desirable impurity.The exemplary impurity preferably avoided is the salt of slaine, particularly alkali metal such as sodium.

Preferably can the mol ratio of refractive index of hardening resin non-heavy metal colloidal sol and heavy metallic oxide precursor be mixed with coupling.This forms vision opacity that is lower and that expect.Preferably, the non-heavy metal oxide (" non-HMO ") represented with non-HMO:HMO is about 0.5:1 to about 10:1 with the molar ratio range of heavy metallic oxide (" HMO "), be more preferably about 3:1 to about 9:1, and be most preferably about 4:1 to 7:1.

In a preferred embodiment, the nanometer particle wherein assembled comprises siliceous and compound that is zirconium, preparation method from silicon dioxide gel and Diacetatozirconic acid. with the mixing of the mol ratio of about 5.5:1.

Before mixing non-heavy metal oxide sol and heavy metallic oxide precursor, preferably reduce the pH of non-heavy metal oxide sol to provide the acid solution of the pH with about 1.5 to about 4.0.Then non-heavy metal oxide sol and the solution comprising heavy metallic oxide precursor are slowly mixed and vigorous stirring.Preferably in whole Blending Processes, carry out vigorous stirring.Then drying is carried out to solution, to remove moisture and other volatile components.Drying realizes by various ways, comprises such as tray dried, fluid bed and spraying dry.In a preferred method, wherein use Diacetatozirconic acid., adopt spray drying method to carry out drying.

The drying material of gained is preferably made up of the hollow ball of less particle substantially spherical in shape and fragmentation.Then calcine to remove remaining Organic substance further to these fragments in batches.The Organic substance of removing remnants makes filler become more frangible, thus causes more effectively reducing particle diameter.In calcination process, cooking temperature is preferably set to about 200 DEG C to about 800 DEG C, is more preferably about 300 DEG C to about 600 DEG C.According to the amount of the material of calcining, heat refining about 0.5 is little of about 8 hours.Preferably, the knit time of calcining step makes to obtain the surface area tended towards stability.Preferably, the time of selection and temperature make the filler of gained for white, not containing black, Lycoperdon polymorphum Vitt or amber particle, as by visual inspection determined.

Then preferably, be that median particle is less than about 5 μm by the ground material calcined, preferably be less than 2 μm (based on volumes), granularity can use the Sedigraph5100 (Mike instrument company (Micrometrics of Georgia State, USA Norcross, Norcross, Ga.)) measure.The proportion that particle size measures by first using Accuracy1330 gravimeter (the Mike instrument company (Micrometrics, Norcross, Ga.) of Georgia State, USA Norcross) to obtain filler performs.Grinding realizes by various method, and these methods comprise such as agitation grinding, vibro-grinding, comminution by gas stream, jet grinding and ball milling.Ball milling is preferred method.

The filler of gained comprises, comprises the nanometer particle of gathering, is substantially made up of the nanometer particle assembled or is made up of the nanometer particle assembled.If needed, verify by transmission electron microscope (TEM).Surface treatment can be carried out to the particle surface of filler (F1).Surface treatment can adopt and realize for the same way of the particle of filler (F2) as detailed below, or according to such as US6,730,156 or technique described in WO01/30304 realize.

Once be dispersed in resin, filler (F1) just remains accumulation shape.That is, this particle is not broken for discrete (that is, independent) and non-associated (that is, non-cohesion, non-agglomerated) particle during dispersion steps.Filler (F1) usually with relative to whole compositions weighing scale at least about 30 % by weight or at least about 35 % by weight or at least about 40 % by weight amount exist.Filler (F1) exists with the highest relative to the weighing scale of whole compositions about 70 % by weight or the highest about 60 % by weight or the highest amount of about 50 % by weight usually.Therefore, filler (F1) exists with the amount of the weighing scale relative to whole compositions about 30 % by weight to about 70 % by weight or about 35 % by weight to about 60 % by weight or about 40 % by weight to about 50 % by weight usually.

Dental composition only can comprise a kind of filler (F1) or multiple filler (F1), such as, and two kinds, three kinds or four kinds of different fillers.Do not wish, by concrete theoretical constraint, to it is believed that filler (F1) contributes to the polishability of dental composition as herein described.It is found that, filler (F1) aggregation of particles body can be broken to contribute to obtaining smooth surface and low light scattering compared to rough surface during polishing step.From Point of View of Clinical, this causes high gloss retention and colour stability usually.

On the contrary, when using non-cohesion filler, use in the example as EP2167013 (A1) those, find its be unfavorable for realize expect wearability.

In addition, use during non-cohesion filler and usually increase along with viscosity.But high viscosity adversely affects the allotter mixing manually driven and the power extruded needed for dental materials.In addition, due to the high-specific surface area of non-cohesion filler, therefore usually the non-cohesion filler of high-load (such as, higher than about 40 % by weight) cannot be introduced in resin matrix.

Therefore, it is found that, the nano-sized filler of assembling is used to contribute to obtaining the dental composition with outstanding wearability, higher amount of filler is obtained in the resin matrix of dental composition, be conducive to preparing paste due to the better wettability of this filler, and contribute to obtaining better treatment characteristic.

Dental composition only can comprise a kind of filler (F2) or multiple filler (F2), such as, and two kinds, three kinds or four kinds of different fillers.Filler (F2) comprises the nanometer particle of cohesion.The chemical property of filler (F2) is not particularly limited, as long as can realize earmarking.The size of filler grain should make it possible to obtain have formed can hardening resin substrate can the homogeneous mixture of hardenable component (A1).

According to an embodiment, the feature of filler (F2) be in following characteristics at least one or all:

The specific surface area of the nanometer particle of-cohesion BET formula of Taylor (special according to Bu Lunuo, Amy and): about 30m ²/ g to about 400m ²/ g or 50m ²/ g to about 300m ²/ g or 70m ²/ g to about 250m ²/ g;

-comprise SiO ₂particle, ZrO ₂particle, Al ₂o ₃particle and their mixture.

If needed, specific surface area can measure according to the method described above.

The nanoparticle of suitable cohesion comprises aerosil, and the goldschmidt chemical corporation (DegussaAG, Hanau, Germany) of such as Hanau, Germany is with trade name Aerosil ^tMproduct sold (such as, AerosilOX-130 ,-150 and-200 and AerosilR8200), with trade name CAB-O-SIL ^tMthe product of the Cabot Co., Ltd (CabotCorp, Tuscola, Ill.) of M5 purchased from American Illinois Ta Sikela and with trade name HDK ^tMsuch as HDK-H2000, HDKH15; HDKH18, HDKH20 and HDKH30 are purchased from the product of Wa Ke company (Wacker).

The surface of the filler grain of filler (F2) can process with resin compatible surface conditioning agent.Particularly preferred surface conditioning agent or coating material comprise can with the silane finish of resin polymerization.Preferred silane treatment reagent comprises γ-metacryloxy propyl trimethoxy silicane, with trade name A-174 from Wei Ke OSi specialized company (Connecticut State Danbury) (WitcoOSiSpecialties (Danbury, Conn.)) buy, and γ-glycidyl ether oxygen propyl trimethoxy silicane, buy from amalgamation scientific & technical corporation (Pennsylvania's Bristol) (UnitedChemicalTechnologies (Bristol, Pa.)) with trade name G6720.

Alternatively, the combination of surface modifier can be used, wherein at least one reagent have can with can the functional group of hardening resin copolymerization.Such as, polymer-based group can be ethylenic unsaturated functional group or the cyclic functionality being easy to ring-opening polymerisation.The unsaturated polymer-based group of ethylenic can be such as acrylate or (methyl) acrylate or vinyl groups.The cyclic functionality being easy to ring-opening polymerisation generally comprises hetero atom, such as oxygen, sulfur or nitrogen, and preferably wraps oxygen containing 3 rings, such as epoxide.Can comprise general not with can other surface modifiers of reacting of hardening resin to improve dispersibility or rheological characteristic.The example of the silane of the type comprises the silane of such as alkyl or aryl polyethers, alkyl, cycloalkyl, hydroxy alkyl, aryl, hydroxyaryl or aminoalkyl-functional.

Do not wish, by concrete theoretical constraint, to it is believed that filler (F2) contributes to the rheological behavior of dental composition as herein described.Use this type of filler to allow to provide high compactedness dental composition, and said composition still can use static mixing head to mix.From Point of View of Clinical, this causes the treatment characteristic improved usually, such as paste be easy to mix and cartridge systems to extrude power lower.Filler (F2) usually with relative to whole compositions weighing scale at least about 1 % by weight or at least about 3 % by weight or at least about 5 % by weight amount exist.Filler (F2) exists with the highest relative to the weighing scale of whole compositions about 20 % by weight or the highest about 15 % by weight or the highest amount of about 10 % by weight usually.Therefore, filler (F2) exists with the amount of the weighing scale relative to whole compositions about 1 % by weight to about 20 % by weight or about 3 % by weight to about 15 % by weight or about 5 % by weight to about 10 % by weight usually.

Dental composition as herein described comprises at least two kinds can hardenable component, i.e. component (A1) and component (A2).Component (A1) and component (A2) are the component of the resin matrix of the dental composition that can in the dark solidify.Dental composition comprises at least one can hardenable component (A1), and this can hardenable component be carbamate (methyl) acrylate with the degree of functionality being at least 2.

If needed, dental composition can comprise at least two kinds, three kinds or four kinds different can hardenable component (A1).The molecular weight of hardenable component (A1) 450 or at least about 800 or at least about 1000 can be at least about.Available scope comprises about 450 to about 3000, about 800 to about 2700 or about 1000 to about 2500.Have higher than about 450g/mol or be usually less than the molecule with lower molecular weight higher than the volatility of the molecule of the molecular weight of about 1000g/mol, therefore can contribute to providing biocompatible composition.

In addition, if molecular weight is not high enough, the rupture strength of the expectation of the dental composition hardened possibly cannot be realized.

Carbamate (methyl) acrylate adopted in compositions as herein described is usually reacted by the compound of NCO-end-blocking and suitable monofunctional (methyl) acrylate monomer and is formed, described monofunctional (methyl) acrylate monomer such as hydroxy ethyl methacrylate, hydroxyethyl meth acrylate, HPMA, preferred hydroxyethyl meth acrylate and HPMA.

Carbamate (methyl) acrylate obtains by various technique known to those skilled in the art.Such as, polyisocyanates and polyhydric alcohol can react to form isocyanate-terminated carbamate prepolymer, and this prepolymer reacts with (methyl) acrylate such as 2-ethoxy (methyl) acrylate subsequently.This type of reaction can be carried out under room temperature or higher temperature, optionally carries out under catalyst such as tin catalyst, tertiary amine etc. exist.

The polyisocyanates that can be used for being formed isocyanate-functional carbamate prepolymer can comprise any organic isocyanate with at least two free isocyanate groups.Comprise aliphatic, alicyclic, aromatics and araliphatic isocyanates.

Any known polyisocyanates can be adopted, the combination of such as alkyl and alkylidene polyisocyanates, cycloalkyl and cycloalkylidene polyisocyanates and such as alkylidene and cycloalkylidene polyisocyanates.

Preferably, use has the vulcabond of chemical formula X (NCO) 2, and wherein X represents the aliphatic hydrocarbon free radical with 2 to 12 C atoms, the clicyclic hydrocarbon free radical with 5 to 18 C atoms, has the aromatic hydrocarbon radical of 6 to 16 C atoms and/or has the araliphatic hydrocarbon free radical of 7 to 15 C atoms.

The example of suitable polyisocyanates comprises: 2, 2, 4-tri-methyl hexamethylene-1, 6-vulcabond, hexa-methylene-1, 6-vulcabond (HDI), cyclohexyl-1, 4-vulcabond, 4, 4'-methylene-bis-(cyclohexyl isocyanate), 1, 1'-methylene-bis-(4-isocyanate group) cyclohexane extraction, isophorone diisocyanate, 4, 4'-methylenediphenyl diisocyanates, 1, 4-tetramethylene diisocyanate, methyl-and p-tetramethyl xylene phenyl diisocyanate, 1, 4-phenylene vulcabond, 2, 6-and 2, 4-toluenediisocyanate, 1, 5-naphthalene diisocyanate, 2, 4'-and 4, 4'-'-diphenylmethane diisocyanate and their mixture.

Also may use and known in multiple-amino ester formate chemistry there is the polyisocyanates of higher functional degree or the polyisocyanates of modification, such as, comprise the polyisocyanates of carbodiimide group, allophanate groups, chlorinated isocyanurates and/or biuret group.Particularly preferred isocyanates is isophorone diisocyanate, 2,4,4-trimethyls-hexamethylene diisocyanate and have the polyisocyanates with isocyanurate structure of higher functional degree.

Isocyanate-terminated carbamate compounds with (methyl) acrylate ended to prepare carbamate (methyl) acrylate compounds.In general, can adopt and there is terminal hydroxy group and any (methyl) acrylic ester type end-capping reagent also with acrylate moiety or methacrylic moieties (preferably there is methacrylic moieties).

The example of suitable end-capping reagent comprises: 2-ethoxy (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, two (methyl) glycerol acrylate and/or trimethylolpropane two (methyl) acrylate.Particularly preferred is HEMA (HEMA) and/or 2-hydroxy ethyl methacrylate (HEA).

In isocyanate groups and compound, the equivalent proportion of reactive aspectant isocyanate groups is 1.1:1 to 8:1, is preferably 1.5:1 to 4:1.Isocyanates polyaddition can be known in polyurethane chemistry catalyst existence under occur, described catalyst is organo-tin compound such as dibutyl tin laurate or amine catalyst such as diazabicylo [2.2.2] octane such as.In addition, synthesis can be carried out in melt or suitable solvent, and this solvent or can add in preparation process before prepolymer preparation.Suitable solvent is alkyl ether and the aromatic hydrocarbon of such as acetone, 2-butanone, oxolane, dioxane, dimethyl formamide, METHYLPYRROLIDONE (NMP), ethyl acetate, ethylene and propylene glycol.Particularly preferably use ethyl acetate as solvent.

The example of suitable carbamate (methyl) acrylate comprises: 7,7,9-trimethyl-4,13-dioxy-3,14-dioxa-5,12-diaza hexadecane-1,16-dioxy base-dimethylacrylate (such as, Plex666-1, ), 7,7,9-trimethyl-4,13-dioxy-5,12-diaza hexadecane-1,16-dioxy-dimethylacrylate (UDMA), derived from Isosorbide-5-Nitrae and 1, the carbamate (methacrylate) (such as, as described in EP0934926A1) of two (1-isocyanate group-1-Methylethyl) benzene of 3-and their mixture.

According to an embodiment, can the feature of hardenable component (A1) as follows:

There is structure A-(-S1-U-S2-MA) _n, wherein

A is the coupling part comprising at least one unit,

S1 is the spacer groups comprising the unit that at least 4 are connected to each other,

S2 is the spacer groups comprising the unit that at least 4 are connected to each other,

The unit of A, S1 and S2 is independently selected from CH ₃-,-CH ₂-,-O-,-S-,-NR ¹-,-CO-,-CR ¹=, -N=,-CR ¹r ²-, wherein R ¹and R ²independently selected from the aryl of the cycloalkyl of the alkyl of hydrogen, alkyl, replacement, thiazolinyl, cycloalkyl, replacement, aryl alkyl, aryl or replacement, wherein these unit can form straight chain, side chain or circulus, such as alkyl, cycloalkyl, aryl, ester group, carbamate groups or amide groups

U is the carbamate groups connecting spacer groups S1 and spacer groups S2,

MA is acrylic or methacrylic acid group, and

N is 3 to 6.

According to an embodiment, compositions can have following structure by hardenable component (A1)

A-(-S1-U-S2-MA) _n

Wherein

A comprises the coupling part at least about 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 unit,

S1 be comprise the unit be connected to each other spacer groups and comprise at least about 4,5,6,7,8,9 or 10 unit,

S2 be comprise the unit be connected to each other spacer groups and comprise at least about 4,5,6,7,8,9,10,12,15,20 or 25 unit,

U is the carbamate groups connecting spacer groups S1 and spacer groups S2,

MA is acrylic or methacrylic acid group, and

N is about 3 to 6 or about 4 to 6 or about 5 to 6.

Can preferably, A has circulus and comprises at least about 6 unit.

Also can preferably, S1 has straight or branched structure and comprises at least about 4 unit or about 6 unit.

Also can preferably, S2 has straight or branched structure and comprises at least about 6 unit or about 8 unit.

Also preferably can adopt hardenable compound (A1), wherein A has circulus and comprises at least about 6 unit, and S1 has linear chain structure and comprises at least about 4 unit, and S2 has linear chain structure and comprises at least about 8 unit, and U is carbamate groups.

The atom of carbamate groups or the atom of (methyl) acrylic that connect S1 and S2 all do not belong to spacer groups S1 or spacer groups S2.Therefore, the atom of carbamate groups disregards the unit making spacer groups S1 or spacer groups S2.

Character and the structure of coupling part are not particularly limited.Coupling part can comprise saturated (without double bond) or unsaturated (having at least one or two double bonds) unit, aromatics or heteroaromatic units (comprising the equiatomic aromatic structure of N, O and S).

The instantiation with the coupling part A of circulus comprises:

The instantiation with the coupling part A of non-annularity branched structure comprises:

The bonding of dotted line instruction and spacer groups S1.

The essence of spacer groups S1 or spacer groups S2 and structure are all not limited especially.

Spacer groups is made up of the unit be connected to each other.Typical unit comprises: CH ₃-,-CH ₂-,-O-,-S-,-NR ¹-,-CO-,-CR ¹=, -N=,-CR ¹r ²-, wherein R ¹and R ²independently selected from the aryl of the cycloalkyl of the alkyl of hydrogen, alkyl, replacement, thiazolinyl, cycloalkyl, replacement, aryl alkyl, aryl or replacement.

These unit can form straight chain, side chain or circulus, such as alkyl, cycloalkyl, aryl, ester group, carbamate groups or amide groups.

The structure of S1 can be identical with the structure of S2.But in certain embodiments, the structure of S1 is different from the structure of S2.In a specific embodiment, the quantity of the unit existed in S1 is less than or equal to the quantity of the unit existed in S2.

In a specific embodiment, S1 can have saturated hydrocarbon structure.

In another specific embodiment, S2 can have saturated hydrocarbon structure.

Typical case for the spacer groups of S1 comprises:

Dotted line instruction is chemically bonded to group A or group U.

Typical case for the spacer groups of S2 comprises:

Dotted line instruction is chemically bonded to (methyl) acrylic or group U.Quantity according to the unit of the present invention's calculating provides in bracket.

Can the instantiation of hardenable component (A1) comprise

In addition, suitable carbamate (methyl) acrylate is based on α, poly-(methyl) acrylate of ω-end-blocking (such as, as described in EP1242493B1) or can be polyester, polyethers, polybutadiene or polycarbonate type carbamate (methyl) acrylate (such as, as described in US6936642B2).

Can hardenable component (A1) usually with relative to whole compositions weighing scale at least about 1 % by weight or at least about 3 % by weight or at least about 4.5 % by weight amount exist.

Can usually exist with the highest relative to the weighing scale of whole compositions about 20 % by weight or the highest about 15 % by weight or the highest amount of about 10 % by weight by hardenable component (A1).

Therefore, can usually exist with the amount of the weighing scale relative to whole compositions about 1 % by weight to about 20 % by weight or about 3 % by weight to about 15 % by weight or about 4.5 % by weight to about 10 % by weight by hardenable component (A1).

It is found that, use hardenable carbamate (methyl) acrylate component and more specifically use said components to be conducive to provide a kind of compositions of sclerosis, the compositions of this sclerosis has sufficiently high pliability, and as contributing to the flexibilizer of the fracture toughness improving the dental composition after solidifying.

Dental composition comprises can hardenable component (A2), and this can hardenable component be (methyl) acrylate of the free redical polymerization with the degree of functionality being at least 2.Component (A1) can be different from by hardenable component (A2), such as, for degree of functionality, chemical part, molecular weight or their combination.Usually carbamate moiety can not comprised by hardenable component (A2).

If needed, dental composition can comprise at least two kinds, three kinds or four kinds different can hardenable component (A2).The molecular weight of hardenable component (A2) 170g/mol can be at least about or at least about 200g/mol or at least about 300g/mol.

Can hardenable component (A2) molecular weight usually about 170g/mol to about 3000g/mol or about 200g/mol to about 2500g/mol or about 300g/mol to about 2000g/mol scope in.

Free radical activity functional group can be had by hardenable component (A2), and comprise monomer, oligomer and the polymer with two or more ethylenically unsaturated group.

This type of free redical polymerization material comprises two-or poly-acrylate and methacrylate, such as glycerol diacrylate, three glycerol acrylate, glycol diacrylate, diethylene glycol diacrylate, TEGDMA, 1, ammediol diacrylate, 1, ammediol dimethylacrylate, trimethylolpropane triacrylate, 1, 2, 4-butantriol trimethyl acrylic ester, 1, 4-cyclohexanediol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, Sorbitol six acrylate, two [1-2-(acryloxy)]-p-ethoxyl phenenyl dimethylmethane, two [1-(3-acryloxy-2-hydroxyl)]-p-propoxyphenyl dimethylmethane, the Polyethylene Glycol of molecular weight 200-500 two-acrylate and two-methacrylate, acrylated monomers can copolymer mixture, such as, at US4,652, those described in 274, and acrylated oligamer, such as, at US4,642, those described in 126, and vinyl compound, such as diallyl phthalate, divinyl succinate ester, vinyl hexanediacetate and phthalic acid divinyl ester.

Preferred ethylenically unsaturated monomers is methacrylate and acrylate monomer, such as: two (methyl) acrylate of propylene glycol, butanediol, hexanediol, ethohexadiol, nonanediol, decanediol and Semen arachidis hypogaeae glycol, two (methyl) acrylate of ethylene glycol, Polyethylene Glycol and polypropylene glycol, two (methyl) acrylate such as 2 of ethoxylated bisphenol A, two (4-(methyl) the acrylic oxygen base tetraethoxy phenyl) propane of 2'-, and (methyl) acrylamide.The monomer used also can be the ester of alpha-cyanoacrylate .beta.-methylacrylic acid, cinnamic acid and sorbic acid.

Also the methacrylate that EP0235826 mentions can be used, such as two [3 [4]-methacryls-oxygen ylmethyl-8 (9)-three ring [5.2.1.0 ^2,6] decyl methyl triglycol ester.Specially suitable example is 2, two-4 (3-methacryloxy-2-propoxyl) phenyl-propane (Bis-GMA) of 2-, 2,2-two-4 (3-methacryloxypropoxy) phenyl-propane, dimethacrylate triethyleneglycol ester (TEGDMA) and two methylol three ring-(5.2.1.0 ^2,6) two (methyl) acrylate of decane.

It is found that, use can hardenable component (A2) and more specifically use said components can be conducive to provide a kind of compositions of sclerosis, the compositions of this sclerosis has sufficiently high mechanical strength, therefore can be used as the cross-linking agent of the mechanical property contributing to the dental composition after improving solidification.

Can hardenable component (A2) usually with relative to whole compositions weighing scale at least about 5 % by weight or at least about 10 % by weight or at least about 15 % by weight amount exist.

Can usually exist with the highest relative to the weighing scale of whole compositions about 60 % by weight or the highest about 50 % by weight or the highest amount of about 45 % by weight by hardenable component (A2).

Therefore, can usually exist with the amount of the weighing scale relative to whole compositions about 5 % by weight to about 60 % by weight or about 10 % by weight to about 50 % by weight or about 15 % by weight to about 45 % by weight by hardenable component (A2).Dental composition as herein described comprises dark curing or redox curing initiator component or system.

The initiator that one class can cause the polymerization of free radical activity functional group comprises conventional chemical initiator system, the combination of such as organic peroxide and amine.These initiators relying on redox reaction are often called " self-curing catalyst ".They provide usually used as two parts system, and in two parts system, reactant (reducing agent and oxidant) is separated from each other and stores then at the forward slip value being about to use.

In other alternate forms, heat can be utilized to cause sclerosis or the polymerization of free radical activity group.The example being suitable for the thermal source of dental materials of the present invention comprises induction, convection current and radiation.Thermal source should be able to produce the temperature of at least 40 DEG C to 150 DEG C under normal operation.This process is preferred for causing the material polymerization carried out beyond oral environment.

Organic peroxide compounds is suitable as Redox initiator systems together with so-called activator.Especially, compound is dilauroyl peroxide such as, and benzoyl peroxide and the p-chlorobenzoyl of peroxidating and the p-toluyl of peroxidating can be considered to organic peroxide compounds.

Be suitable as activator: such as aryl tertiary amine, such as from US3,541, N known to 068, N-be two-(hydroxyalkyl)-3,5-dimethylaniline and N, N-pair-(hydroxyalkyl)-3,5-bis--tert-butyl aniline, especially N, N-pair-([β]-oxygen-butyl)-3,5-bis--tert-butyl aniline and N, N-is two-(hydroxyalkyl)-3,4,5-trimethylaniline.

Suitable activator also can be barbiturates as described in US2003/008967, DE1495520 and barbituric acid derivatives and as US4, the malonyl sulfur amide described in 544,742 (corresponding EP0059451).Preferred malonyl sulfonamide is 2; 6-dimethyl-4-isobutyl group malonyl sulfonamide, 2; 6-diisobutyl-4-propyl group malonyl sulfonamide, 2; 6-dibutyl-4-propyl group malonyl sulfonamide, 2; 6-dimethyl-4-ethyl malonyl sulfonamide and 2,6-dioctyl-4-isobutyl group malonyl sulfonamide.For further acceleration, polymerization is preferably carried out under the existence of heavy metal compound and ionizing halogen or pseudohalogen.

Heavy metal is applicable to using with the form of soluble organic compounds.Equally, halide ion and Pseudohalides are applicable to using with the form of soluble-salt, as can called after solubility ammonium chloride and quaternary ammonium chloride compound in example.Suitable activator especially metal, from ferrum to cuprio group, the complex of preferably copper and ferrum and the complex of especially copper.Heavy metal preferably adopts the form of soluble organic compounds.It is suitable that such as ferric carboxylate, copper carboxylate, ferritin salt, cuprein salt, copper naphthenate, Schweinfurt green and iron naphthenate.

Described by other suitable redox initiation systems have in the paper (Prog.Polym.Sci. the 8th volume 61-131 page (1982)) of the people such as G.Misra.For the reason of storage life, the dark curing component of initiator system needs to store Oxidizing and Reducing Agents separately.Therefore, dental composition as herein described provides with the form of two parts system usually.

In the base component that some components (being called hereinafter (X)) of dark curing system are included in assembly cover box or paste, in the catalyst member that some components (being called hereinafter (Y)) of dark curing system are included in assembly cover box or paste.

The representative instance being included in the dark curing initiator component (X) in base component comprises salt acid amide (such as, hydrochloric acid dibutyl phenethyl amine) and cupric component is (such as, copper (II)-bis-(1-phenyl pentamethyl-1,3-diketone) complex).The representative instance being included in the dark curing initiator component (Y) in catalyst member comprises: comprise the component of barbiturates acid moieties (such as; 1-benzyl-5-phenyl-barbituric acid) and malonyl sulfonamide, peroxide (such as; tert-butyl hydroperoxide-3; 5,5-trimethyl cyclohexane).

If needed, except dark curing initiator component, dental composition as herein described also can comprise visible-light curing initiator component.

This type of initiator is being exposed to wavelength at about 400nm to the free radical that usually can produce during luminous energy about between 800nm for being polymerized.The example of visible-light curing initiator component comprises the system such as based on amine and α-diketone.Suitable system is described in such as US4,071,124 and WO2009151957 in.The content of these documents is incorporated to herein all by reference.

In addition, dental composition also can comprise at least one or whole in following component:

Plasticizer,

X-ray visible particles,

Additive.

It is optional for adding plasticizer components.

Addible plasticizer generally includes not containing the component of polymerizable moiety.The example of available plasticizer comprises: polyethyleneglycol derivative, polypropylene glycol, dibutyl-, dioctyl-, dinonyl-and diphenyl phthalate, form ester by adipic acid, decanedioic acid and citric acid, phosphate ester is tricresyl phosphate such as, paraffin oil, triacetyl glycerine, ethyoxyl and propoxyl group bisphenol-A diacetate esters, silicone oil, and their mixture.

The molecular weight of plasticizer is usually in the scope of about 200g/mol to about 2500g/mol or about 300g/mol to about 2000g/mol.When it is present, plasticizer exists with the amount of the weighing scale relative to whole compositions about 0.1 % by weight to about 10 % by weight or about 0.5 % by weight to about 7.5 % by weight or about 1 % by weight to about 5 % by weight usually.Use plasticizer usually can be conducive to the preparation of compositions, when especially compositions should provide with paste form.

In dental composition, add X-ray visible particles is favourable, because these particles can make practitioner differentiate better, the dental materials in patient oral cavity also distinguishes healthy dentistry tooth structure and dental prosthesis material.This dental materials becomes ray can not be saturating.

The ray impermeability of dental materials is favourable in some situation using X-roentgenodiagnosis situations of teeth.Such as, ray can not allow the detection to the secondary dental caries that may have been formed around implant at dental tissue by material thoroughly.The required degree of ray impermeability may change, and this depends on that embody rule and practitioner assess the expectation of x-ray film.

Suitable X-ray visible particles comprises metal oxide particle and metal fluoride particle.Preferably may have oxide or the fluoride of the heavy metal of the atomic number being greater than about 28.The selection of heavy metallic oxide or fluoride should make not give the less desirable color of its hardening resin be scattered in or light and shade.Such as, ferrum and cobalt are disadvantageous, because they apply the contrast color of the neutral color of teeth of dead color and dental materials.More preferably, heavy metallic oxide or fluoride are oxide or the fluoride of the metal with the atomic number being greater than 30.Suitable metal-oxide is yttrium, the oxide of strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, stannum, zinc, lanthanide series (namely having the element of the atomic number in the scope of 57 to 71 (comprising end value)), cerium and their combination.Suitable metal fluoride is such as borontrifluoride yttrium and borontrifluoride ytterbium.Most preferably, in material of the present invention, the oxide having and be greater than 30 but be less than the heavy metal of the atomic number of 72 and fluoride is optionally comprised.Particularly preferred ray can not comprise lanthana, zirconium oxide, yittrium oxide, ytterbium oxide, Barium monoxide, strontium oxide, cerium oxide and their combination by metal-oxide thoroughly.Other suitable filler increasing ray impermeability are the salt of barium and strontium, especially strontium sulfate and barium sulfate.Heavy metallic oxide or metal fluoride particle can be passed through surface treatment.

The particle mean size of X-ray visible particles (being in non-agglomerated state) is usually in the scope of about 20 to about 500 or about 50 to about 300nm.When it is present, X-ray visible particles exists with the amount of the weighing scale relative to whole compositions about 0.1 % by weight to about 15 % by weight or about 1 % by weight to about 10 % by weight or about 2 % by weight to about 5 % by weight usually.

Other additives optionally added can comprise blocker, antimicrobial, pigment, dyestuff, can photobleaching colorant, stabilizing agent and Fluoride release material.

The example of spendable pigment and dyestuff comprises titanium dioxide or zinc sulfide (Griffith's zinc white .), red iron oxide 3395, Bayferrox920Z Huang, blue 807 (dyestuffs based on C.I. Pigment Blue 15) of Neazopon or the yellow ER of HelioFast.These additives can be used for the independent dyeing of dental composition.

What can exist the example of photobleaching colorant can comprise rose-red, methylene-violet, methylene blue, fluorescein, Yihong Huang, Eosin Y, ethyl Yihong, Yihong indigo plant, eosin scarlet, Erythrosin B, erythrosine yellow blend, toluidine blue, 4', 5'-dibromofluorescein and their blend.Other example of photobleaching colorant can be found in US6,444, in 725.The color of compositions of the present invention also can be given by sensitizer.

The example of the fluoride releasing agent that can exist comprises the fluoride mineral of natural existence or synthesis.These fluoride sources optionally process with surface conditioning agent.Other additives that can add comprise stabilizing agent, especially free radical scavenger, such as replace and/or unsubstituted hydroxy aromatic compound (such as Yoshinox BHT (BHT), hydroquinone, hydroquinone monomethyl ether (MEHQ), 3, 5-bis--tertiary butyl-4-hydroxy methyl phenyl ethers anisole (2, 6-bis--tert-butyl group-4-thanatol), 2, 6-bis--tert-butyl group-4-(dimethylamino) methylphenol or 2, 5-bis--t-butylhydroquinone or 2-(2'-hydroxyl-5'-aminomethyl phenyl)-2H-benzotriazole, 2-(2'-hydroxyl-5'-uncle-octyl phenyl)-2H-benzotriazole, oxybenzone (UV-9), 2-(2'-hydroxyl-4', 6'-bis--uncle-amyl group phenyl)-2H-benzotriazole, the n-octyloxybenzophenone of 2-hydroxyl-4-, 2-(2'-hydroxyl-5'-first acrylyl oxy-ethyl phenyl)-2H-benzotriazole, phenothiazine and HALS (hindered amine type light stabilizer).This analog assistant optionally comprises reactive part, make they will with resin copolymerization.

Suitable blocker is such as 1,2-halogenated diphenyl ether.Other additives addible comprise absorbent, emulsifying agent, antioxidant and wetting agent.Absolute needs are not had to the existence of these auxiliary agents or additive, therefore auxiliary agent or additive can not exist.But if existed, they exist with the amount harmless to expection object usually.

The available quantity of additive comprises:

At least about 0.1 % by weight or at least about 0.5 % by weight or at least about 1 % by weight and/or

At the most about 15 % by weight or at the most about 10 % by weight or at the most about 5 % by weight.

Typical scope comprises about 0.1 % by weight to about 15 % by weight or about 0.5 % by weight to about 10

% by weight or about 1 % by weight to about 5 % by weight.

The all components used in dental composition as herein described all should have enough biocompatibility, that is, said composition should not produce toxicity, harmful or immunoreation in living tissue.Compositions as herein described does not usually comprise and is selected from following component:

Zero such as higher than about 5 % by weight the polymerizable components of amount, this polymerizable components comprises acidic-group,

Zero such as higher than about 5 % by weight simple function (methyl) acrylate of amount,

Zero such as higher than about 5 % by weight the solvent of amount,

Zero such as higher than about 5 % by weight the acid reaction filler of amount,

Zero such as higher than about 10 % by weight or the filler grain of amount higher than about 5 % by weight, and this filler grain has the particle mean size of about 1 μm to about 100 μm,

Zero such as higher than about 10 % by weight or the non-cohesion nano-sized filler of amount higher than about 5 % by weight,

And their mixture.

That is, these components usually can not add arbitrarily and therefore not with the weighing scale relative to whole compositions higher than about 10 % by weight higher than about 8 % by weight or higher than about 5 % by weight or higher than about 2 % by weight amount exist.

But different according to the raw material selected, possibly cannot invariably sometimes, and compositions can comprise the vestige of any one said components.

The example of usual non-existent acid reaction filler comprises aluminum fluoride glass (sometimes also referred to as GIZ glass), the hydroxide of alkaline-earth metal, oxide and carbonate as Ca (OH) ₂, Mg (OH) ₂, CaO, MgO, CaCO ₃, MgCO ₃.

The such as characteristic such as polishability and gloss retention adversely may be affected to add the filler with the particle mean size of above-mentioned scope higher than the amount of about 10 % by weight.

The example of this type of filler comprises aluminum fluoride glass, quartz and ground glass, water-fast fluoride such as CaF ₂, cristobalite, calcium silicates, zeolite (comprising molecular sieve), oxide powder such as aluminium oxide or zirconium oxide or their mixed oxide, barium sulfate, calcium carbonate.This type of filler adding high-load adversely may affect the performance attractive in appearance of the dental composition of sclerosis.

The example of usual non-existent solvent comprises the saturated of straight chain, side chain or ring-type or unsaturated alcohols, ketone, esters or has two or more the mixture of solvent of described type of 2 to 10 C atoms, as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, THF, acetone, methyl ethyl ketone, Hexalin, toluene, alkane and alkyl acetate.

Dental composition as herein described can comprise the component of following amount:

Filler (F1): about 30 % by weight to about 70 % by weight or about 35 % by weight to about 60 % by weight,

Filler (F2): about 1 % by weight to about 20 % by weight or about 3 % by weight to about 15 % by weight,

Can hardenable component (A1): about 1 % by weight to about 20 % by weight or about 3 % by weight to about 15 % by weight or about 4.5 % by weight to about 10 % by weight,

Can hardenable component (A2): about 5 % by weight to about 60 % by weight or about 10 % by weight to about 50 % by weight or about 15 % by weight to about 45 % by weight,

Dark curing initiator component: about 0.1 % by weight to about 5 % by weight or about 0.3 % by weight to about 4 % by weight or about 0.5 % by weight to about 3 % by weight,

Plasticizer: about 0.1 % by weight to about 10 % by weight or about 0.5 % by weight to about 7.5 % by weight or about 1 % by weight to about 5 % by weight,

X-ray visible particles: about 0.1 % by weight to about 15 % by weight or about 1 % by weight to about 10 % by weight or about 2 % by weight to about 5 % by weight,

Additive: about 0.1 % by weight to about 15 % by weight or about 0.5 % by weight to about 10 % by weight or about 1 % by weight to about 5 % by weight,

% is relative to the weight of whole compositions.

Compositions as herein described provides with the form of two parts compositions usually.

Wherein a part is commonly referred to base component, and another part is then commonly referred to catalyst member.When these two parts combine, obtain the compositions of sclerosis.

If various piece provides with paste form, then the viscosity of each paste (uses physics flow graph to record under 23 DEG C and shear rate 30L/s) usually in the scope of about 1Pa*s to about 100Pa*s or about 10Pa*s to about 75Pa*s.

Therefore, according to another embodiment, dental composition provides with the form of assembly cover box, and this assembly cover box comprises base component (A) and catalyst member (B),

Base component (A) comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

-can hardenable component (A1),

-can hardenable component (A2),

-dark curing initiator component (X),

% by weight relative to the weight of base component,

Catalyst member (B) comprises

-filler (F2),

-dark curing initiator component (Y),

Dark curing initiator component (X) and dark curing initiator component (Y) form Redox initiator systems.

According to another embodiment, dental composition as herein described describes with the form of assembly cover box, and this assembly cover box comprises base component (A) and catalyst member (B),

Base component (A) comprises

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

The amount of-Yue 1 % by weight to about 20 % by weight can hardenable component (A1),

The amount of-Yue 5 % by weight to about 60 % by weight can hardenable component (A2),

-dark curing initiator component (X),

% by weight relative to the weight of base component,

And catalyst member (B) comprises

The filler (F2) of-Yue 1 % by weight to about 20 % by weight,

-dark curing initiator component (Y),

% by weight relative to the weight of catalyst member,

Dark curing initiator component (X) and dark curing initiator component (Y) form Redox initiator systems.

According to another embodiment, dental composition provides with the form of assembly cover box, and this assembly cover box comprises base component (A) and catalyst member (B),

Base component (A) comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

-can hardenable component (A1),

-can hardenable component (A2),

-dark curing initiator component (X),

% by weight relative to the weight of base component,

Catalyst member (B) comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

-can hardenable component (A1),

-can hardenable component (A2),

-dark curing initiator component (Y),

% by weight relative to the weight of catalyst member,

Dark curing initiator component (X) and dark curing initiator component (Y) form Redox initiator systems,

Base component A or catalyst member B does not all comprise any one in following component:

The polymerizable components of-amount higher than about 5 % by weight, this polymerizable components comprises acidic-group,

Simple function (methyl) acrylate of-amount higher than about 5 % by weight,

The solvent of-amount higher than about 5 % by weight,

The acid reaction filler of-amount higher than about 5 % by weight,

The filler grain of-amount higher than about 10 % by weight, this filler grain has the particle mean size of about 1 μm to about 100 μm.

Except filler and dark curing initiator component, catalyst member (B) optionally comprises plasticizer to be conducive to preparing paste.Spendable plasticizer is described above.

In certain embodiments, can in the dark solidify or by the compositions of redox reaction solidification meet in following parameter at least one or more, sometimes all:

Working time: about 30s to about 1.5 minutes or about 45s to about 1 minute,

Fixing time: about 2.5 minutes to about 6 minutes or about 3 minutes to about 5 minutes,

Bending strength after solidification: about 50MPa to about 200MPa (measuring according to ISO4049),

Work to break after solidification: about 5KJ/m ²to about 15KJ/m ²,

Impact strength after solidification: about 5KJ/m ²to 15KJ/m ²(measuring according to ISO179-1),

Wearing and tearing after solidification: be less than about 20mm ³or be less than about 15mm ³or be less than about 10mm ³(method according to EXAMPLEPART is measured).

In certain embodiments, the combination of following feature is expected: high bending strength, high work to break and low abrasion.If needed, above-mentioned feature can be determined according to described in following instance part.

Compositions as herein described is prepared by mixing its corresponding component.Mixing is usually by using plant equipment to realize, and this plant equipment comprises can purchased from the super mixer of such as German Hauschild+CoKG or dissolvers.Filler component mixes with powder or particulate forms usually.If needed, first filler component can be distributed in the liquid composition of compositions.

On the other hand, the present invention relates to the assembly cover box comprising dental composition as herein described, this assembly cover box provides with paste/paste form and is filled in the chamber of two-chamber cartridge or two independent syringes, and comprises with at least one in lower component or whole:

Dental impression material,

Dental cement,

Binding agent.

In use, two-chamber cartridge is equipped with static mixing head usually, and the device being used as mixing and sending.The volume ratio of chamber (I) and chamber (II) usually in the scope of about 1:1 to about 20:1, especially preferably in the scope of 1:1 to about 10:1.Available cartridge case is described in US2007/0090079 or US5, and 918, in 772, the disclosure of these patents is incorporated herein by reference.Operable cartridge case can be commercially available from the Sulzer chemical company (SulzerMixpacAG, Switzerland) of Switzerland.Available static mixing head is described in US2006/0187752 or US5,944, and in 419, the disclosure of these patents is incorporated herein by reference.Operable mixing head can be commercially available from the Sulzer chemical company (SulzerMixpacAG, Switzerland) of Switzerland.

Due to selected formula, dental composition as herein described can be easy to use manual actuation geared system to carry out mixing and sending from two-chamber cartridge as known in the art.Alternatively, but less preferably, paste/paste compositions as herein described can the form of two independent syringes to provide and various paste can hand mix before the use.If needed, for determining to need the power of extruding applied whether to be in acceptable scope, can test as follows:

To the volume (volume ratio is from 1:1 to 10:1) of 50mL be had and the two-chamber cartridge comprising catalyst and base paste is equipped with mixing head (SulzerMixpac) and plunger, then be placed in the keeper of the universal tester (ZwickZ010) being equipped with 10KN force cell.In order to extrude dental composition, push rod is set according to the mode pushing plate of plunger being applied to power.The speed of push rod is adjusted to 25mm/ minute.If the power >2N (software textXpertV8.1) of record, then start to record data.When pushing plate/push rod move forward in cartridge case altogether 20mm time terminate measure.Be considered to acceptable lower than about 1000N or lower than about 800N or lower than the power of extruding of about 600N.If the power of extruding exceeds specific value, then the automixte system of manual actuation cannot be used fully to extrude and blend compositions.

The example of operable dental impression material comprises the silicone compositions based on the material of alginate, polyethers technology, the silicone compositions (such as, VPS material) of addition-curable and condensation curable.

The silicone compositions of addition-curable and curable polyether material are preferred sometimes, because they have outstanding performance and the accuracy of Geng Gao.

Dental impression material is usually by following characteristics, multiple or all characterize:

Denseness (according to ISO4823): 0,1,2,3,

Fixing time: at ambient conditions after (such as 23 DEG C) mixing in about 15 minutes,

Xiao A hardness is (according to ISO4823; 24h): at least about 20 or at least about 40,

Hot strength (according to DIN53504): at least about 0.2MPa or at least about 3.0MPa,

Elongation at break (according to DIN53504): at least about 30% or at least about 150% or at least about 200%,

Recoverable force (according to ISO4823): at least about 90% or at least about 95% or at least about 98%.

Suitable dental impression material also at EP2072029B1, US6,677,393, EP1512724B1, US6,127,449, WO2008/014224 and US5,569, described by having in 691.The content of these documents is incorporated to herein all by reference.The commercially available acquisition of dental impression material, such as, with brand Impregum ^tMor Imprint ^tMpurchased from 3MESPE.The dental composition of sclerosis being fixed to dental structure surface to be repaired uses binding agent and/or dental cement usually.

Essence and the characteristic of binding agent and/or dental cement are not particularly limited, as long as can realize the result expected.Especially preferred is binding agent and self-adhesive dental resin cement.Binding agent or self-adhesive dental resin cement system comprise polymerisable monomer, the acidic components optionally comprising polymerizable moiety, filler, optional alkaline filler and Redox initiator systems usually.

Suitable cement is also described in WO2007/140440 (A2), US2010/0016466, US2004/0110864.The content of these documents is incorporated to herein all by reference.Binding agent and the commercially available acquisition of self-adhesive dental resin cement, such as, with brand RelyX ^municem or RelyX ^tMultimate is purchased from 3MESPE.

Dental composition as herein described can be used as chronicity or persistency corona and bridge material particularly.Chronicity corona and bridge material can be directly placed in mouth and in-situ solidifying (sclerosis), or can make the outer artificial tooth of mouth and the appropriate location sticked to subsequently in mouth.

This dental composition also can be used for preparing insert, onlay, veneer or being used as packing material in bulk.On the other hand, the present invention relates to the method preparing chronicity or persistency corona or bridge, the method comprises the step in mould compositions as herein described being placed into setting dental impression material.Dental impression material can be alginate, siloxanes (VPS) or polyether impression dental materials.

The alginate impression material of commercially available acquisition comprises Palgat ^tM(3MESPE).The silicone impression material of commercially available acquisition comprises Express ^tM, Imprint ^tMand Position ^tM(3MESPE).The polyether of commercially available acquisition comprises Impregum ^tM(3MESPE).

One or more during the canonical process of dental procedure comprises the following steps:

A) use dental impression material to prepare the die of hard toothing to be repaired, thus obtain the former of tooth structure,

B) wait for until dental impression material setting,

C) from hard toothing, setting dental impression material is removed,

D) curable compositions as herein described is placed in the former of dental impression material,

E) former of filling is repositioned onto on tooth structure to be repaired,

F) wait for until curable compositions solidifies at least in part, said composition can be removed from tooth structure to be repaired, and preparation or the tooth structure that is shaped does not leave the residue of said composition,

G) from setting impression material, remove the compositions of solidification,

H) dental cement is used the compositions removed to be fixed on tooth structure to be repaired with bonding way.

The full content of patent prospectus, patent documentation and the publication quoted herein is incorporated to herein, all by reference in full as each file is quoted separately.

There is provided following instance so that the present invention to be described.

example

Except as otherwise noted, otherwise all numbers and percentage ratio are all by weight, and all water is deionized water, and all molecular weight are weight average molecular weight.In addition, except as otherwise noted, otherwise all experiments all environmental condition (23 DEG C; 1013 millibars) under carry out.

measure

bending strength and work to break

The assay method of bending strength is: use the sample with 2*2*25mm size to carry out three-point bending strength test according to ISO4049.Work to break can be calculated based on the data obtained.Work to break is with [kJ/m ²] provide for unit.Bending strength with [MPa] for unit provides.

abrasion

Abrasion [mm ³] measuring method as follows:

Abrasion test employing gradient is that the particular sample of 30 ° is carried out.For this purpose, material to be filled in the depression of M12Inbus screw rod and to be cured according to the explanation of manufacturer.

Use the diamond saw of 75 μm to be polished by sample and preserve 4 days in distilled water at 36 DEG C.Then start to adopt following condition simulation to chew:

Masticatory force: 80N; Lateral movement: 4mm; Sliding motion: 10mm; Antagonist: Talcum ball; Chewing cycle number of times: 1200000; Times of thermal cycle (5/55 DEG C): 5000.

After carrying out chaw simulation, measure abrasion by using the loss of laser scanning microscope VK-X200 (Keyemce company (KeyenceCompany)) measurement volumes.

About the more information of abrasion test is found in paper Materialpr ü fung39 (1997) the 77-80 page of the people such as M.Rosentritt.

compositions

abbreviation

table 1

assemble the Representative synthetic procedures of filler (F1):

Zr/Si nanocluster fillers, according to US6, is prepared described in 730,156B1 the 25th row preparation example A.The filler grain obtained is according to US6, and the method described in the preparation example B of 730,156B1 carries out surface treatment.

prepare the general process of dental composition:

Super mixer (Hausschild) is used corresponding component to be mixed.Base paste and catalyst paste are all filled in two-chamber cartridge (SulzerMixpac).Cartridge case is installed static mixing head (SulzerMixpac) and uses the geared system of manual actuation to distribute said composition.The mixing ratio of base paste and catalyst paste is 10:1 in example 1 and 2 and comparative example 1-3, and is 1:1 in example 3.Analyze the characteristic of the paste of solidification.Result is shown in Table 8.

example 1:

table 2

comparative example 1:

(using non-cohesion Nano filling)

table 3

comparative example 2:

(compared with comparative example 1, using the non-cohesion nanoparticle of more high-load)

table 4

example 2:

table 5

comparative example 3:

(not the preparation of amido-containing acid ester (methyl) acrylate)

table 6

example 3:

(1:1 preparation)

table 7

table 8

result:

Example 1-3 shows high bending strength and work to break and low abrasion value.In comparative example 1, use non-cohesion Nano filling to also obtain high work to break, but wear-corrosion resistance is poor, because amount of filler is limited.In comparative example 2, increase preparation that non-cohesion Nano filling obtains cannot re-use static mixer compared to example 1-3 and carry out distributing and mixing.Do not use the comparative example 3 of carbamate (methyl) acrylate to show lower mechanical property and lower fracture work value, show that it has certain fragility.

Claims (15)

1. a dental composition, it comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight, described filler comprises the nanometer particle of gathering,

The filler (F2) of-Yue 1 % by weight to about 20 % by weight, described filler comprises the nanometer particle of cohesion,

-can hardenable component (A1), described can hardenable component be have the degree of functionality carbamate (methyl) acrylate with the molecular weight of about 400g/mol to about 3000g/mol that are at least 2,

-can hardenable component (A2), describedly can be at least 2 and (methyl) acrylate being different from the free redical polymerization of the degree of functionality of component (A1) for having by hardenable component,

-redox curing initiator system,

Described dental composition does not comprise the non-cohesion nano-sized filler of amount higher than about 10 % by weight, and % by weight relative to the weight of described whole compositions.

2. the dental composition according to aforementioned claim, the feature of filler (F1) be in following characteristics at least one or all:

-specific surface area: about 50m ²/ g to about 400m ²/ g,

-comprise and be selected from SiO ₂, ZrO ₂and the particle of their mixture.

3. according to dental composition in any one of the preceding claims wherein, the feature of filler (F2) be in following characteristics at least one or all:

-specific surface area: about 30m ²/ g to about 400m ²/ g,

-comprise and be selected from SiO ₂, ZrO ₂, Al ₂o ₃and the particle of their mixture.

4., according to dental composition in any one of the preceding claims wherein, describedly can be selected from by hardenable component (A1):

There is structure A-(-S1-U-S2-MA) _ncompound

A is the coupling part comprising at least one unit,

S1 is the spacer groups comprising the unit that at least 4 are connected to each other,

S2 is the spacer groups comprising the unit that at least 4 are connected to each other,

U is the carbamate connecting spacer groups S1 and spacer groups S2,

MA is acrylic or methacrylic acid group,

N is 3 to 6,

The unit of described A, S1 and S2 is independently selected from CH ₃-,-CH ₂-,-O-,-S-,-NR ¹-,-CO-,-CR ¹=, -N=,-CR ¹r ²-,

Wherein R ¹and R ²independently selected from the aryl of the cycloalkyl of the alkyl of hydrogen, alkyl, replacement, thiazolinyl, cycloalkyl, replacement, aryl alkyl, aryl or replacement, wherein these unit can form straight chain, side chain or circulus, such as alkyl, cycloalkyl, aryl, ester group, carbamate groups or amide groups

And their mixture.

5. according to dental composition in any one of the preceding claims wherein, describedly can be selected from by hardenable component (A2): glycerol diacrylate, three glycerol acrylate, glycol diacrylate, diethylene glycol diacrylate, TEGDMA, 1, ammediol diacrylate, 1, ammediol dimethylacrylate, trimethylolpropane triacrylate, 1, 2, 4-butantriol trimethyl acrylic ester, 1, 4-cyclohexanediol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, Sorbitol six acrylate, two [1-2-(acryloxy)]-p-ethoxyl phenenyl dimethylmethane, two [1-(3-acryloxy-2-hydroxyl)]-p-propoxyphenyl dimethylmethane, the ethylene glycol of molecular weight 200-500, Polyethylene Glycol and polypropylene glycol two-acrylate and two-methacrylate, two (methyl) acrylate of Ethoxylated bisphenol A, 2,2'-two (4-(methyl) propylene acyloxy tetraethoxy phenyl) propane, two [3 [4]-methacrylic acid groups-oxygen methyl-8 (9)-three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems methyl triethanol acid esters, 2,2-two-4 (3-methacrylic acid group oxygen propyl group) phenylpropyl alcohol alkane, two methylol three ring-(5.2.1.0 ^2,6) two (methyl) acrylate of decane and their mixture.

6., according to dental composition in any one of the preceding claims wherein, described redox curing initiator system comprises the component being selected from peroxide, the component comprising barbituric acid moiety, malonyl sulfonamide moiety and their mixture.

7., according to dental composition in any one of the preceding claims wherein, it also comprises at least one or whole in following component:

Plasticizer,

X-ray visible particles,

Pigment,

Additive, described additive is selected from blocker, antimicrobial, stabilizing agent, Fluoride release material, absorbent, emulsifying agent, antioxidant and wetting agent, dyestuff and their mixture.

8. according to dental composition in any one of the preceding claims wherein, comprise plasticizer, described plasticizer is selected from the component comprising following material: polyalkylene glycol moiety, polypropylene glycol, dibutyl-, dioctyl-, dinonyl-and diphenyl phthalate, adipate ester, sebacate and citrate, paraffin oil, glyceryl triacetate, ethoxylated bisphenol A diacetate esters and propoxyl group bisphenol-A diacetate esters and silicone oil and their mixture.

9. according to dental composition in any one of the preceding claims wherein, it is characterized in that in following parameter at least one or all:

Zero working time: about 30s extremely about 1.5 minutes,

Zero fixing time: about 2.5 minutes to about 6 minutes,

Bending strength after zero solidification: about 50MPa to about 200MPa, measures according to ISO4049,

Work to break after zero solidification: about 5KJ/m ²to about 15KJ/m ²,

Impact strength after zero solidification: about 5KJ/m ²to 15KJ/m ², measure according to ISO179-1,

Abrasion after zero solidification: be less than about 20mm ³.

10., according to dental composition in any one of the preceding claims wherein, it does not comprise at least one or whole in following component:

Zero higher than about 5 % by weight the polymerizable components of amount, described polymerizable components comprises acidic-group,

Zero higher than about 5 % by weight simple function (methyl) acrylate of amount,

Zero higher than about 5 % by weight the solvent of amount,

Zero higher than about 5 % by weight the acid reaction filler of amount,

Zero higher than about 10 % by weight the filler grain of amount, described filler grain has the particle mean size of about 1 μm to about 100 μm,

Zero higher than about 10 % by weight the non-cohesion nano-sized filler of amount,

And their mixture.

11. according to dental composition in any one of the preceding claims wherein, and its feature is as follows:

The amount of filler (F1): about 30 % by weight to about 70 % by weight,

The amount of filler (F2): about 1 % by weight to about 20 % by weight,

Can the amount of hardenable component (A1): about 1 % by weight to about 20 % by weight,

Can the amount of hardenable component (A2): about 5 % by weight to about 60 % by weight,

% by weight relative to the weight of described whole compositions.

12. according to dental composition in any one of the preceding claims wherein, and described dental composition provides with the form of assembly cover box, and described assembly cover box comprises base component (A) and catalyst member (B),

Base component (A) comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

-can hardenable component (A1),

-can hardenable component (A2),

-dark curing initiator component (X),

% by weight relative to the weight of described base component,

Catalyst member (B) comprises

-filler (F2),

-dark curing initiator component (Y),

Described dark curing initiator component (X) and described dark curing initiator component (Y) form Redox initiator systems.

13. according to dental composition in any one of the preceding claims wherein, and described dental composition provides with the form of assembly cover box, and described assembly cover box comprises base component (A) and catalyst member (B),

Base component (A) comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

The amount of-Yue 1 % by weight to about 20 % by weight can hardenable component (A1),

The amount of-Yue 5 % by weight to about 60 % by weight can hardenable component (A2),

-dark curing initiator component (X),

% by weight relative to the weight of described base component,

Catalyst member (B) comprises:

The filler (F1) of the amount of-Yue 30 % by weight to about 70 % by weight,

The filler (F2) of the amount of-Yue 1 % by weight to about 20 % by weight,

-dark curing initiator component (Y),

% by weight relative to the weight of described catalyst member,

Dark curing initiator component (X) and dark curing initiator component (Y) form Redox initiator systems,

Described base component (A) or described catalyst member (B) all do not comprise any one in following component:

Zero higher than about 5 % by weight polymerizable components, described polymerizable components comprises acidic-group,

Zero higher than 5 % by weight simple function (methyl) acrylate,

Zero higher than about 5 % by weight the solvent of amount,

Zero higher than about 5 % by weight acid reaction filler,

Zero higher than about 10 % by weight the filler grain of amount, described filler grain has the particle mean size of about 1 μm to about 100 μm,

Zero higher than about 10 % by weight the non-cohesion nano-sized filler of amount.

14. comprise according to dental composition in any one of the preceding claims wherein or according to the assembly cover box described in claim 12 or 13 and with at least one in lower component or whole assemblies cover box:

Dental impression material,

Dental cement,

Binding agent.

15. use according to dental composition in any one of the preceding claims wherein as or for the preparation of corona, bridge, insert, onlay, veneer and packing material in bulk.